Ethyl acetosuccinate

CH3C(0Na)=CHC02C2H5 + C2H5OH CH3C(0Na)=CHC02C2H5 + CICH2CO2C2H5 

Submitted by Homer Adkins, Neville Isbell, and Brono WojaK. 

In a 3-I. three-necked, round-bottomed flask fitted with a mechanical stirrer, reflux condenser, and separatory funnel is placed 400 cc. of absolute alcohol (Note i). Through the condenser tube is added slowly, 23 g. (i gram atom) of dean sodium cut into thin slices. The completion of the reaction is hastened by heating the flask on a steam bath. When the sodium has dissolved completely, 143 g. (i.i moles) of ethyl acetoacetate is introduced slowly. Alter starting the mechanical stirrer, 123 g. (i mole) of ethyl chloroacetate (Note 2) is added slowly over a period of an hour, and the reaction mixture is refluxed for five to six hours. At this point the reaction mixture should no longer give an alkaline reaction with moist litmus. 

A good grade of absolute alcohol is required. For this purpose ordinary absolute alcohol may be dried by treating with a little sodium, adding a few cubic centimeters of ethyl succinate, and distilling directly into the reaction flask (see also Org. Syn. Coll. Vol. i, 255). 

Ethyl chloroacetate boiling at 142-145° was used. This ester can be prepared readily by refluxing for six hours a mixture of 200 g. of chloroacetic acid, 120 g. of absolute alcohol, and 25 g. of concentrated sulfuric acid. The product is purified in the conventional way, and the yield is 185 g. (70 per cent of the theoretical amount). 

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Ethyl acetosuccinate has been prepared by the interaction of ethyl sodio-acetoacetate and ethyl chloroacetate or broino-acetate. The method given above is a modification of that given by Conrad. ... 

Ethyl acetosuccinate, 14, 38 Ethyl fl-acetotricarballylate, 14, 39 Ethyl adipate, 17, 30, 32... 

Shah, R. H. Shah, N. M. Condensation of a-substituted acetoacetates with phenols. VI. The condensation of phenols with ethyl acetosuccinate. J. Indian Chem. Soc. 1942,19,481 85. 

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